4-Bromothioanisole → HCID 22923284, compound

HRID 2258344Notes

Reaction equation

HRID 2258344 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8][CH3:9])=[CH:4][CH:3]=1.C([Li])CCC.[Si:15]([O:22][C:23]1[CH:24]=[C:25]([CH:28]=[CH:29][CH:30]=1)[CH:26]=[O:27])([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16]>O1CCCC1.CCCCCC>[CH3:9][S:8][C:5]1[CH:6]=[CH:7][C:2]([CH:26]([C:25]2[CH:28]=[CH:29][CH:30]=[C:23]([O:22][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:16])[CH3:17])[CH:24]=2)[OH:27])=[CH:3][CH:4]=1

Participants

6

Reactant 3

HCID 660374-BromothioanisoleHCID 112071113-(t-Butyldimethylsilyloxy)benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 22923284HCID 22923284, compoundYield 99%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of 4-bromothioanisole (10.0 g, 49.0 mmol) in 60 mL of anhydrous tetrahydrofuran was cooled to -78° C. under nitrogen and 32 mL (49 mmol) of 1.55M n-butyllithium in hexane was was added dropwise at a rate to maintain temperature below -60° C. The reaction was stirred an additional 15 minutes after addition was complete, and a solution of crude 3-(tert-butyldimethylsilyloxy)benzaldehyde (11.6 g, 49 mmol) in 50 mL of dry tetrahydrofuran was added dropwise over 20 minutes. The reaction was stirred another 30 minutes and quenched at -78° C. with saturated aqueous ammonium chloride. After warming to room temperature, the reaction was diluted with 200 mL of diethyl ether and washed with 50 mL of water and 50 mL of saturated aqueous sodium chloride. After drying over sodium sulfate, the solvent was removed to give 17.5 g (99%) of crude (4-methylthio-phenyl)(3-tert-butyldimethylsilyloxyphenyl)methanol as an orange oil.

Workup

  1. temperatureto maintain temperature below -60° C
  2. additionafter addition
  3. stirringThe reaction was stirred another 30 minutes
  4. customquenched at -78° C. with saturated aqueous ammonium chloride
  5. additionthe reaction was diluted with 200 mL of diethyl ether
  6. washwashed with 50 mL of water and 50 mL of saturated aqueous sodium chloride
  7. dry with materialAfter drying over sodium sulfate
  8. customthe solvent was removed

Sources & evidence

ORD record
ord-8becee90862e4d87bbbb236a1e3c42bc
Source dataset
uspto-grants-1997_08
Patent number
US05658908

Reaction notes

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